Composition including quantum dot, manufacturing method quantum dot and color filter

ABSTRACT

A photosensitive resin composition includes: (A) a binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a quantum dot surface-modified with a compound having a thiol group at one terminal end and an alkoxy group, a cycloalkyl group, a carboxyl group, or a hydroxy group at the other terminal end; and (E) a solvent. A curable composition includes: (A′) a resin; (B′) a quantum dot surface-modified with a compound represented by Chemical Formula 1 or Chemical Formula 2; and (C′) a solvent. A method of manufacturing the surface-modified quantum dot, and a color filter manufactured using the photosensitive resin composition or the curable composition are also disclosed.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.16/155,691, filed Oct. 9, 2018, which claims priority to and the benefitof Korean Patent Application Nos. 10-2017-0141376 and 10-2018-0023867filed in the Korean Intellectual Property Office on Oct. 27, 2017 andFeb. 27, 2018, respectively, the entire contents of each of which areincorporated herein by reference.

BACKGROUND 1. Field

This disclosure relates to a composition including a surface-modifiedquantum dot, a method of manufacturing the surface-modified quantum dot,and a color filter manufactured by using the composition. In addition,the composition according to this disclosure may be applied to a thermalcuring process such as an inkjet process as well as a lithographicprocess, and thus, a composition including a surface-modified quantumdot according to embodiments of the present disclosure has a wide rangeof processability.

2. Description of the Related Art

In general, a color filter applied to a display is formed by using aphotosensitive resist composition, forming a desired pattern through anexposure process by using a photomask, and then, dissolving and removinga non-exposed region through a development process. A material for thecolor filter may be desired or required to have properties ofalkali-solubility, high sensitivity, adherence to a substrate, chemicalresistance, heat resistance, and the like. However, the material for thecolor filter in general is not suitably or sufficiently cured throughthe exposure and thus should be thermally cured through a heat treatmentat a high temperature of greater than or equal to 200° C. in order toobtain suitable or required characteristics. Accordingly, the materialfor the color filter has a limit in being applied to electronic paper,OLED, and the like that are formed using a low temperature process.

On the other hand, an attempt to complement the unsuitable orinsufficient curing characteristics by adding a compound, for example,epoxide, peroxide, and the like thereto to develop a photosensitiveresin composition for a color filter using a relatively low temperatureprocess for the electronic paper, the OLED, and the like has been madebut does not secure suitable or sufficient curing and thus has a problemof low reliability.

The problem occurs, since a color material such as a pigment, a dye, orthe like competitively absorbs light energy with a photopolymerizationinitiator, and in addition, the photosensitive resin composition may nothave suitable or sufficient initiation efficiency and accordingly, showa lower curing rate of a photopolymerizable monomer than one not usingthe color material, since the pigment and the dye remove a radicalproduced therein.

Accordingly, an effort to develop a composition including a quantum dotinstead of a dye or a pigment which is capable of remarkably improvingreliability such as chemical resistance, heat resistance, and the likeis being continuously made by using a different material instead of theexisting color material such as a dye, a pigment, or the like.

In addition, new various methods have been used that are capable ofreplacing an existing pigment dispersion method such as, for example, aninkjet printing method. The inkjet printing method is a method offorming a light-blocking layer such as a black matrix and the like on aglass substrate and injecting ink into the pixel space. The inkjetprinting method does not require a separate process such as coating, anexposure, a development, and the like during the manufacture of a colorfilter and thus may reduce an amount of material required or used inthese processes.

When an inkjet ink in the inkjet printing method is used to manufacturea color filter, at least two kinds of pigments are generally mixed tosecure desired or required color characteristics. For example, adiketopyrrolopyrrole-based red pigment, for example, C.I. Pigment Red254 in a red filter is adopted as a main pigment. In addition, ananthraquinone-based red pigment, for example, C.I. Pigment Red 177 or anisoindolinone-based yellow pigment, for example, C.I. Pigment Yellow 139is generally added as an auxiliary pigment. However, other yellow andorange pigments, for example, C.I. Pigment Yellow 138, C.I PigmentYellow 150, C.I. Pigment Orange 38, and the like may be added ifnecessary or desired. These pigments have excellent colorcharacteristics, light resistance, and heat resistance and have beenused as a material for a color filter, but as a LCD color filter hasrecently been more widely used, a higher property level has been beingincreasingly desired or required. Accordingly, research on atomizationand fine dispersion of the pigments to improve color characteristicssuch as brightness and color purity during the transmission is beingmade, but there is a limit in realizing the color characteristics of acolor filter by actually combining these pigments.

SUMMARY

An embodiment provides a composition including a quantum dot, whichmaintains a high photo-conversion rate even after it goes through acolor filter manufacturing process and is suitable or appropriate for alithography method and a thermally-curing inkjet printing method.

Another embodiment provides a method of manufacturing a surface-modifiedquantum dot dispersible in a suitable solvent for a display process suchas a color filter and the like.

Another embodiment provides a color filter manufactured by using thecomposition including a quantum dot.

A composition according to an embodiment is a photosensitive compositionthat includes (A) a binder resin; (B) a photopolymerizable monomer; (C)a photopolymerization initiator; (D) a quantum dot surface-modified witha first compound having a thiol group at one terminal end or at themiddle of a main chain and having an alkoxy group, a cycloalkyl group, acarboxyl group, or a hydroxy group at the other terminal end or a secondcompound having each thiol group at one terminal end and at the middleof the main chain and having an alkoxy group, a cycloalkyl group, acarboxyl group, or a hydroxy group at the other terminal end; and (E) asolvent.

The alkoxy group may be a C1 to C10 alkoxy group and the cycloalkylgroup may be a C3 to C10 cycloalkyl group.

The first compound and the second compound may each independentlyinclude an ester group.

The first compound may be represented by Chemical Formula 1 and thesecond compound may be represented by Chemical Formula 2.

In Chemical Formula 1 and Chemical Formula 2,

-   -   R¹ is a substituted or unsubstituted C1 to C20 alkyl group, a        substituted or unsubstituted C1 to C20 alkoxy group, a        substituted or unsubstituted C3 to C20 cycloalkyl group, a        substituted or unsubstituted C6 to C20 aryl group, or a        substituted or unsubstituted lactone ring,    -   L¹ and L² are independently a single bond, a substituted or        unsubstituted C1 to C20 alkylene group, a substituted or        unsubstituted C1 to C20 oxyalkylene group, or a combination        thereof, and    -   n is an integer of 1 or 2.

The lactone ring may be a 5-membered ring or a 6-membered ring.

In Chemical Formula 2, L² may be a C1 to C20 alkylene group substitutedwith a thiol group.

The substituted or unsubstituted C1 to C20 oxyalkylene group may be asubstituted or unsubstituted oxymethylene group, a substituted orunsubstituted oxyethylene group, or a combination thereof.

The oxymethylene group may be represented by Chemical Formula 3 and theoxyethylene group may be represented by Chemical Formula 4.

In Chemical Formula 3 and Chemical Formula 4,

-   -   m is an integer of 1 to 5.

The first compound may be represented by one of Chemical Formula 1-1 toChemical Formula 1-7 and the second compound may be represented byChemical Formula 2-1.

-   -   (in Chemical Formula 1-3 to Chemical Formula 1-6, m is an        integer of 1 to 5)

The surface-modified quantum dot may have a core-shell structure, theshell may include Zn, and a thiol group at the terminal end of thecompound represented by Chemical Formula 1 or Chemical Formula 2 may bebonded with the Zn of the shell.

The quantum dot may have a maximum fluorescence photoluminescencewavelength in a wavelength range of 500 nm to 680 nm.

The solvent may include propylene glycol monomethylether acetate,dipropylene glycol methylether acetate, ethanol, ethyleneglycoldimethylether, ethylene diglycolmethylethylether, diethyleneglycoldimethylether, 2-butoxyethanol, N-methylpyrrolidine,N-ethylpyrrolidine, propylene carbonate, γ-butyrolactone, or acombination thereof.

The binder resin may include an acryl-based binder resin, a cardo-basedbinder resin, or a combination thereof.

The photosensitive composition may further include a (F) diffusionagent.

The diffusion agent may be included in an amount of 0.1 wt % to 20 wt %based on the total amount (total weight) of the photosensitivecomposition.

The diffusion agent may include barium sulfate, calcium carbonate,titanium dioxide, zirconia, or a combination thereof.

The photosensitive composition may include 1 wt % to 30 wt % of the (A)binder resin; 0.1 wt % to 30 wt % of the (B) photopolymerizable monomer;0.1 wt % to 10 wt % of the (C) photopolymerization initiator; 1 wt % to40 wt % of the (D) surface-modified quantum dot; and a balance amount ofthe (E) solvent based on the total amount (total weight) of thephotosensitive composition.

The photosensitive composition may further include malonic acid;3-amino-1,2-propanediol; a silane-based coupling agent; a levelingagent; a fluorine-based surfactant; a polymerization inhibitor; or acombination thereof.

A composition according to another embodiment as a curable compositionincludes (A′) a resin; (B′) a quantum dot surface-modified with thecompound represented by Chemical Formula 1 or Chemical Formula 2; and(C′) a solvent.

The surface-modified quantum dot is the same as described above.

The (C′) solvent may include propylene glycol monomethylether acetate,dipropylene glycol methylether acetate, ethanol, ethyleneglycoldimethylether, ethylene diglycolmethylethylether, diethyleneglycoldimethylether, dimethyl acetamide, 2-butoxyethanol,N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate,γ-butyrolactone, or a combination thereof.

The (A′) resin may include a binder resin and a reactive unsaturatedcompound.

The binder resin may include an acryl-based resin, an epoxy resin, or acombination thereof.

The curable composition may further include a diffusion agent.

The diffusion agent may be included in an amount of 0.1 wt % to 20 wt %based on the total amount (total weight) of the curable composition.

The diffusion agent may include barium sulfate, calcium carbonate,titanium dioxide, zirconia, or a combination thereof.

The curable composition may further include a polymerization initiator.

The polymerization initiator may include a cation initiator.

The curable composition may include, 1 wt % to 40 wt % of the (A′)resin; 1 wt % to 40 wt % of the (B′) surface-modified quantum dot; and abalance amount of the (C′) solvent based on the total amount (totalweight) of the curable composition.

The curable composition may further include malonic acid;3-amino-1,2-propanediol; a silane-based coupling agent; a levelingagent; a fluorine-based surfactant; a polymerization inhibitor; or acombination thereof.

A method of manufacturing the surface-modified quantum dot includesdispersing quantum dots surface-modified with oleic acid in a nonpolarsolvent; adding a compound having a thiol group at one terminal end andan alkoxy group, a cycloalkyl group, a carboxyl group, or a hydroxygroup at the other terminal end, and a metal salt thereto and stirringthe same; and centrifuging the stirred solution to separate asupernatant and lower liquid followed by drying the lower liquid.

The metal salt may be ZnCl₂.

The stirring may be performed at a temperature of 60° C. to 70° C.

Another embodiment provides a method of manufacturing a pixel for acolor filter, the method including: coating the curable composition on asubstrate by an inkjet spraying method to form a pattern; and curing thepattern.

Another embodiment provides a color filter manufactured by using thecomposition, for example the photosensitive composition or the curablecomposition.

The color filter manufactured by using the curable composition mayinclude the pixel for the color filter manufactured by the method ofmanufacturing the pixel.

Other embodiments of the present disclosure are included in thefollowing detailed description.

The surface-modified quantum dot dispersible in a solvent is used in acolor filter manufacturing process including an exposure, a development,curing, and the like, and thus, deterioration of absolute quantumefficiency of the quantum dot in the photosensitive composition may beminimized or reduced and a high photo-conversion rate after alithography process may be maintained.

In addition, a curable composition suitable or appropriate for inkjetprinting does not require an additional process such as coating,exposure, development, and the like, and uses the surface-modifiedquantum dot dispersible in a solvent generally used in the color filtermanufacturing process as a colorant, and thus, may minimize or reducedeterioration of absolute quantum efficiency of the quantum dots in thecurable composition and maintains a high photo-conversion rate after thethermal curing process.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, together with the specification, illustrateembodiments of the subject matter of the present disclosure, and,together with the description, serve to explain principles ofembodiments of the subject matter of the present disclosure.

FIG. 1 is an image of a stirred solution after stirring a compound forsurface-modifying a quantum dot (a compound having a thiol group at oneterminal end and an alkoxy group, a cycloalkyl group, a carboxyl group,or a hydroxy group at the other terminal end) and a metal salt inquantum dots surface-modified with oleic acid and a nonpolar solvent for12 hours at room temperature (20° C.).

FIG. 2 is an image of a stirred solution after stirring a compound forsurface-modifying a quantum dot (a compound having a thiol group at oneterminal end and an alkoxy group, a cycloalkyl group, a carboxyl group,or a hydroxy group at the other terminal end) and a metal salt inquantum dots surface-modified with oleic acid and a nonpolar solvent for12 hours at 65° C.

DETAILED DESCRIPTION

Hereinafter, embodiments of the present disclosure are described in moredetail. However, these embodiments are exemplary, the present disclosureis not limited thereto and the scope of the present disclosure isdefined by the scope of the appended claims, and equivalents thereof.

As used herein, when a specific definition is not otherwise provided,the term “alkyl group” refers to a C1 to C20 alkyl group, the term“alkenyl group” refers to a C2 to C20 alkenyl group, the term“cycloalkenyl group” refers to a C3 to C20 cycloalkenyl group, the term“heterocycloalkenyl group” refers to a C3 to C20 heterocycloalkenylgroup, the term “aryl group” refers to a C6 to C20 aryl group, the term“arylalkyl group” refers to a C6 to C20 arylalkyl group, the term“alkylene group” refers to a C1 to C20 alkylene group, the term “arylenegroup” refers to a C6 to C20 arylene group, the term “alkylarylenegroup” refers to a C6 to C20 alkylarylene group, the term “heteroarylenegroup” refers to a C3 to C20 heteroarylene group, and the term“alkoxylene group” refers to a C1 to C20 alkoxylene group.

As used herein, when a specific definition is not otherwise provided,the term “substituted” refers to replacement of at least one hydrogen bya substituent of a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 toC20 alkoxy group, a nitro group, a cyano group, an amine group, an iminogroup, an azido group, an amidino group, a hydrazino group, a hydrazonogroup, a carbonyl group, a carbamyl group, a thiol group, an estergroup, an ether group, a carboxyl group or a salt thereof, a sulfonicacid group or a salt thereof, a phosphoric acid or a salt thereof, a C1to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynylgroup, a C6 to C20 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 toC20 heterocycloalkynyl group, a C3 to C20 heteroaryl group, or acombination thereof. As used herein, the terms “combination thereof” and“combinations thereof” may refer to a chemical combination (e.g., analloy or chemical compound), a mixture, or a laminated structure ofcomponents.

As used herein, when a specific definition is not otherwise provided,the term “hetero” refers to one substituted with at least one heteroatom of N, O, S and P, in a chemical formula.

As used herein, when a specific definition is not otherwise provided,the term “(meth)acrylate” refers to both “acrylate” and “methacrylate”,and the term “(meth)acrylic acid” refers to “acrylic acid” and“methacrylic acid”.

As used herein, when a specific definition is not otherwise provided,the term “combination” refers to mixing or copolymerization.

As used herein, unless a specific definition is otherwise provided, ahydrogen atom is bonded at the position when a chemical bond is notdrawn where supposed to be given. For example, in the chemical formulaeillustrated herein, hydrogen atoms may be omitted from the chemicalformulae for clarity.

In the present disclosure, a cardo-based resin refers to a resinincluding at least one functional group selected from Chemical Formula100-1 to Chemical Formula 100-11.

As used herein, when a specific definition is not otherwise provided,the symbol “*” indicates a point where the same or different atom orChemical Formula is linked.

A composition according to an embodiment is a photosensitive compositionthat includes (A) a binder resin; (B) a photopolymerizable monomer; (C)a photopolymerization initiator; (D) a quantum dot surface-modified witha first compound having a thiol group at one terminal end or at themiddle of a main chain and having an alkoxy group, a cycloalkyl group, acarboxyl group, or a hydroxy group at the other terminal end or a secondcompound having each thiol group at one terminal end and at the middleof the main chain and having an alkoxy group, a cycloalkyl group, acarboxyl group, or a hydroxy group at the other terminal end; and (E) asolvent.

The composition including a quantum dot includes a photopolymerizablemonomer, a binder resin, a photopolymerization initiator, a solvent, anadditive, and the like. For example, the composition may include anysuitable component of a photosensitive composition generally used in theart, but includes a quantum dot (and a diffusion agent) instead of apigment or a dye, and thus, converts incident blue light after formedinto a film. The quantum dot, which plays an important role in the bluephoto-conversion, is surrounded with a hydrophobic ligand, and eachcomponent of the composition is used to balance for stable dispersion ofthe quantum dot in the composition to which a hydrophilic solvent otherthan the ligand is applied. Herein, luminous efficiency of the quantumdot in the composition is determined depending on which composition (orcomponent) is directly combined on the surface of the quantum dot. Inaddition, since a luminous efficiency loss of the quantum dot in apattern formation process (a thermal process, an exposure process) ischanged depending on the ligand that is directly bonded on (or to) thesurface of the quantum dot or a component of the composition, a ligandor a composition capable of stably passivating the surface of thequantum dot is used to realize high photo-conversion efficiency of acomposition including a quantum dot.

When the composition including a quantum dot is applied to form a panel,the panel goes through several processes after a photoresist process,sometimes under very severe or harsh conditions. During these processes,a layer formed from the composition including a quantum dot may havedamage from oxygen, moisture, heat, and the like, and thus, aphoto-conversion function may sharply deteriorate over time. A quantumdot obtained through an initial synthesis has absolute quantumefficiency of greater than or equal to 80% to 90%, and the efficiencydecreases through the processes of manufacturing a color filter, andthus, reaches 30% to 40% and then, down to 5% to 20% as the followingthermal process is repeated. Accordingly, it is important to maintainhigh absolute quantum efficiency (PLQY) after all the manufacturingprocesses in technology of a quantum dot-applied color filter.

A method of increasing photo-conversion efficiency and a photomaintenance rate of the composition including a quantum dot is to add athiol-based organic material having strong binding affinity with thequantum dot. However, when the thiol-based additive is simply mixed inthe composition, this monomolecular additive pursues a kind ofequilibrium state of repetitive departures and recombinations from thesurface of the quantum dot during formulation of the quantumdot-containing photosensitive resin composition, and this repetitivedeparture and recombination process decreases quantum efficiency.Subsequently, the departures and recombinations of the thiol-basedadditive from the surface of the quantum dot is accelerated through athermal process such as pre-baking and thus promotes the quantumefficiency decrease and resultantly, deteriorates a photo-conversionrate. In addition, the photo-conversion rate may be further deterioratedafter the final post-baking, since a physical loss of the ligand fromthe surface of the quantum dot is increased due to a reaction betweenthiol and an acrylate-based monomer, as a pattern-forming processproceeds

In addition, an attempt to apply a monomer having a set or particularfunctional group or a binder resin to the composition including aquantum dot has been made to increase a photo-conversion rate and aphoto maintenance rate. However, the monomer or the binder resin in amonomolecular state is mostly added to the composition but does notfundamentally block departure of a ligand from the surface of a quantumdot. In order to solve this problem, an attempt to apply an oligomer ora polymer having a multi-functional thiol functional group to firmlypassivate the surface of a quantum dot has been made but still did notsuitably or satisfactorily suppress (or reduce) the deterioration of aphoto-conversion rate.

Meanwhile, the photosensitive composition according to an embodiment mayminimize or reduce deterioration of a photo-conversion rate by using aquantum dot surface-modified with a first compound having a thiol groupat one terminal end or at the middle of a main chain and having analkoxy group, a cycloalkyl group, a carboxyl group, or a hydroxy groupat the other terminal end or a second compound having each thiol groupat one terminal end and at the middle of the main chain and having analkoxy group, a cycloalkyl group, a carboxyl group, or a hydroxy groupat the other terminal end.

Hereinafter, each component is described in more detail.

(D) Surface-Modified Quantum Dot

A quantum dot synthesized according to an existing synthesis method hasa ligand system including (or consisting of) a long alkyl chain havinghydrophobicity and a head group having hydrophilicity (e.g., carboxylicacid, phosphine, amine, phosphine-oxide, etc.). This ligand stabilizes adangling bond on the surface of a quantum dot and applies stability tothe quantum dot itself and concurrently (e.g., simultaneously),dispersibility of the quantum dot as inorganic particles to ahydrophobic solvent.

However, since the ligand system is not changed as desired according toa quantum dot synthesis condition, the quantum dot is dispersed only ina hydrophobic nonpolar solvent and thus may be limitedly applied to adisplay process. Currently, a ligand of an InP-based quantum dot mostlyincludes oleic acid, trioctylamine, trioctylphosphine (-oxide), and thelike, and a solvent in which the quantum dot is dispersed includeshexane, cyclohexane, chloroform, toluene, and the like, which aredesignated as a toxic material due to human toxicity in all the displayprocesses and have unsuitable or inappropriate properties (e.g., amelting point, a boiling point, a vapor pressure, compatibility withother solvents, and the like) apart from the ones used or requiredduring the process.

While the present disclosure is not limited by any particular mechanismor theory, it has been found that hydrophobic and hydrophilic cyclohexylacetate (CHA) as a solvent in which a quantum dot (oleic acid is aligand of the quantum dot) is dispersed by using commercially availableoleic acid in order to solve this problem, but CHA has a unique smell,which causes hardship to workers during the process, and in addition,when the quantum dot is dispersed in CHA and then, stored for a longtime, both dispersibility and storage stability are all deteriorated,and thus photo-conversion efficiency is deteriorated. Accordingly,technology of well dispersing a quantum dot and maintaining excellentdispersibility and photo-conversion efficiency for a long time isdesired or required, and accordingly, technology of modifying thesurface of the quantum dot with a compound having a thiol group at oneterminal end or at the middle of a main chain and having an alkoxygroup, a cycloalkyl group, a carboxyl group, or a hydroxy group at theother terminal end or a compound having each thiol group at one terminalend and at the middle of the main chain and having an alkoxy group, acycloalkyl group, a carboxyl group, or a hydroxy group at the otherterminal end is developed.

Dispersibility of the quantum dot in a suitable solvent for a displayprocess (e.g., a hydrophobic polar solvent) is improved or optimized byusing a thiol group having affinity for the surface of the quantum dotto substitute (ligand-exchange) oleic acid on the surface of the quantumdot and in addition, including an alkoxy group, a cycloalkyl group, acarboxyl group, or a hydroxy group at the terminal end of the thiolgroup-containing compound. In addition, the compound modifying thesurface of the quantum dot has only one thiol group at the terminal endor at the middle of a main chain (monodendrite) may further improvedispersibility about an organic solvent compared with a compound havingat least two thiol groups (polydendrite).

The compound modifying the surface of the quantum dot has a thiol groupat one terminal end or at the middle of a main chain and an alkoxygroup, a cycloalkyl group, a carboxyl group, or a hydroxy group at theother terminal end, wherein the alkoxy group may be a C1 to C10 alkoxygroup and the cycloalkyl group may be a C3 to C10 cycloalkyl group.

For example, the first compound modifying the surface of the quantum dotrepresented by Chemical Formula 1 may be represented by one of ChemicalFormula 1-1 to Chemical Formula 1-8 and the second compound modifyingthe surface of the quantum dot represented by Chemical Formula 2 may berepresented by Chemical Formula 2-1.

In Chemical Formula 1 and Chemical Formula 2,

-   -   R¹ is a substituted or unsubstituted C1 to C20 alkyl group, a        substituted or unsubstituted C1 to C20 alkoxy group, a        substituted or unsubstituted C3 to C20 cycloalkyl group, a        substituted or unsubstituted C6 to C20 aryl group, or a        substituted or unsubstituted lactone ring,    -   L¹ and L² are independently a single bond, a substituted or        unsubstituted C1 to C20 alkylene group, a substituted or        unsubstituted C1 to C20 oxyalkylene group, or a combination        thereof, and    -   n is an integer of 1 or 2.

The lactone ring may be a 5-membered ring or a 6-membered ring.

In Chemical Formula 2, L² may be a C1 to C20 alkylene group substitutedwith a thiol group.

The substituted or unsubstituted C1 to C20 oxyalkylene group may be asubstituted or unsubstituted oxymethylene group, a substituted orunsubstituted oxyethylene group, or a combination thereof.

The oxymethylene group may be represented by Chemical Formula 3 and theoxyethylene group may be represented by Chemical Formula 4.

In Chemical Formula 3 and Chemical Formula 4,

-   -   m is an integer of 1 to 5.

-   -   (in Chemical Formula 1-3 to Chemical Formula 1-6, m is an        integer of 1 to 5.)

For example, a curable composition according to an embodiment may usecompounds represented by Chemical Formula A-1 to Chemical Formula A-11in addition to the compounds represented by Chemical Formula 1 andChemical Formula 2 as a surface-modifying compound.

The surface-modified quantum dot may have a core-shell structure whereinthe shell includes Zn, and the thiol group at the terminal end of thecompound represented by Chemical Formula 1 or Chemical Formula 2 may bebonded with the Zn of the shell.

For example, the quantum dot may absorb light in a wavelength region of360 nm to 780 nm, for example 400 nm to 780 nm and emit fluorescence ina wavelength region of 500 nm to 700 nm, for example, 500 nm to 580 nm,or 600 nm to 680 nm. In some embodiments, the quantum dot may have amaximum fluorescence wavelength (fluorescence λ_(em)) in a wavelengthrange of 500 nm to 680 nm.

The quantum dot may independently have a full width at half maximum(FWHM) in a range of 20 nm to 100 nm, for example, 20 nm to 50 nm. Whenthe quantum dot has a full width at half maximum (FWHM) within theranges, the quantum dot has high color purity, and thus, an effect ofincreasing color reproducibility when used as a color material in acolor filter.

The quantum dot may independently be an organic material, an inorganicmaterial, or a hybrid (mixture) of the organic material and theinorganic material.

The quantum dot may independently include a core and a shell surroundingthe core, and herein, the core and the shell may have a structure suchas a core independently including Group II-IV, Group III-V, and thelike, a core/a shell, a core/a first shell/a second shell, an alloy, analloy/a shell, and the like but are not limited thereto.

For example, the core may include at least one material selected fromCdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, GaN, GaP, GaAs, InP,InAs, and an alloy thereof but is not necessarily limited thereto. Theshell surrounding the core may include at least one material selectedfrom CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, HgSe, and an alloythereof but is not necessarily limited thereto.

In an embodiment, since an interest in protecting the environment hasbeen recently much increased around the world, and regulations of toxicmaterials also have been increased and/or fortified, a non-cadmium-basedlight emitting material (InP/ZnS, InP/ZeSe/ZnS, etc.) having little lowquantum efficiency (quantum yield) but being environmentally-friendlyinstead of a light emitting material having a cadmium-based core isused, but not necessarily limited thereto.

The quantum dot having a core/shell structure may have an entire size(e.g., may have a total average particle diameter) including the shell(an average particle diameter) of 1 nm to 15 nm, for example, 5 nm to 15nm.

For example, the quantum dot may independently include a red quantumdot, a green quantum dot, or a combination thereof. The red quantum dotmay independently have an average particle diameter of 10 nm to 15 nm.The green quantum dot may independently have an average particlediameter of 5 nm to 8 nm.

On the other hand, for dispersion stability of the quantum dot, aphotosensitive resin composition according to an embodiment may furtherinclude a dispersing agent. The dispersing agent helps uniform (e.g.,substantially uniform) dispersibility of a photo-conversion materialsuch as a quantum dot in the photosensitive resin composition and mayinclude a non-ionic, anionic, or cationic dispersing agent. For example,the dispersing agent may be polyalkylene glycol or esters thereof, apolyoxy alkylene, a polyhydric alcohol ester alkylene oxide additionproduct, an alcohol alkylene oxide addition product, a sulfonate ester,a sulfonate salt, a carboxylate ester, a carboxylate salt, an alkylamide alkylene oxide addition product, an alkyl amine and the like, andthey may be used alone or in a mixture of two or more. The dispersingagent may be used in an amount of 0.1 wt % to 100 wt %, for example 10wt % to 20 wt % relative to a solid content of the photo-conversionmaterial such as a quantum dot.

The surface-modified quantum dot may be included in an amount of 1 wt %to 40 wt %, for example 3 wt % to 30 wt % based on the total amount(total weight) of the photosensitive composition. When thesurface-modified quantum dot is included within the foregoing ranges, aphoto-conversion rate is improved and excellent processability may beprovided by not decreasing pattern characteristics and developmentcharacteristics.

(A) Binder Resin

The binder resin may include an acryl-based binder resin, a cardo-basedbinder resin, or a combination thereof.

The acryl-based binder resin is a copolymer of a first ethylenicunsaturated monomer and a second ethylenic unsaturated monomer that iscopolymerizable therewith, and may be a resin including at least oneacryl-based repeating unit.

The first ethylenic unsaturated monomer is an ethylenic unsaturatedmonomer including at least one carboxyl group and examples of themonomer include acrylic acid, methacrylic acid, maleic acid, itaconicacid, fumaric acid, or a combination thereof.

The first ethylenic unsaturated monomer may be included in an amount of5 wt % to 50 wt %, for example, 10 wt % to 40 wt % based on the totalamount (total weight) of the acryl-based binder resin.

The second ethylenic unsaturated monomer may be an aromatic vinylcompound such as styrene, α-methylstyrene, vinyl toluene,vinylbenzylmethylether and the like; an unsaturated carboxylate estercompound such as methyl(meth)acrylate, ethyl(meth)acrylate,butyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, benzyl(meth)acrylate, cyclohexyl(meth)acrylate,phenyl(meth)acrylate, and the like; an unsaturated amino alkylcarboxylate ester compound such as 2-aminoethyl(meth)acrylate,2-dimethylaminoethyl(meth)acrylate, and the like; a carboxylic acidvinyl ester compound such as vinyl acetate, vinyl benzoate, and thelike; an unsaturated glycidyl carboxylate ester compound such asglycidyl(meth)acrylate, and the like; a vinyl cyanide compound such as(meth)acrylonitrile and the like; an unsaturated amide compound such as(meth)acrylamide, and the like; and the like, and may be used alone oras a mixture of two or more.

Examples of the acryl-based binder resin may be apolybenzylmethacrylate, (meth)acrylic acid/benzylmethacrylate copolymer,a (meth)acrylic acid/benzylmethacrylate/styrene copolymer, a(meth)acrylic acid/benzylmethacrylate/2-hydroxyethylmethacrylatecopolymer, a (meth)acrylicacid/benzylmethacrylate/styrene/2-hydroxyethylmethacrylate copolymer,and the like, but are not limited thereto, and may be used alone or as amixture of two or more.

A weight average molecular weight of the acryl-based binder resin may be5,000 g/mol to 15,000 g/mol. When the acryl-based binder resin has aweight average molecular weight within the foregoing range,close-contacting properties to a substrate, physical and chemicalproperties are improved, and a viscosity is suitable or appropriate.

An acid value of the acryl-based binder resin may be 80 mg KOH/g to 130mg KOH/g. When the acryl-based binder resin has an acid value within theforegoing range, excellent resolution of a pixel may be obtained.

The cardo-based binder resin may include a repeating unit represented byChemical Formula 100.

In Chemical Formula 100,

-   -   R¹¹ and R¹² are independently a hydrogen atom or a substituted        or unsubstituted (meth)acryloyloxy alkyl group,    -   R¹³ and R¹⁴ are independently a hydrogen atom, a halogen atom,        or a substituted or unsubstituted C1 to C20 alkyl group,    -   Z¹ is a single bond, O, CO, SO₂, CR¹⁷R¹⁸, SiR¹⁹R²⁰ (wherein, R¹⁷        to R²⁰ are independently a hydrogen atom or a substituted or        unsubstituted C1 to C20 alkyl group), or one of linking groups        represented by Chemical Formula 100-1 to Chemical Formula        100-11,

-   -   (in Chemical Formula 100-5,    -   R^(a) is a hydrogen atom, an ethyl group, C₂H₄Cl, C₂H₄OH,        CH₂CH═CH₂, or a phenyl group.)

-   -   Z² is an acid anhydride residual group, and    -   t1 and t2 are independently an integer in a range of 0 to 4.

A weight average molecular weight of the cardo-based binder resin may be500 g/mol to 50,000 g/mol, for example 1,000 g/mol to 30,000 g/mol. Whenthe weight average molecular weight of the cardo-based binder resin iswithin the foregoing ranges, a suitable or satisfactory pattern may beformed without a residue during a manufacture of a photosensitiveorganic film and without losing a film thickness during development.

The cardo-based binder resin may include a functional group representedby Chemical Formula 101 at at least one terminal end of both terminalends.

In Chemical Formula 101,

-   -   Z³ is represented by Chemical Formula 101-1 to Chemical Formula        101-7.

-   -   (in Chemical Formula 101-1, R^(b) and R^(c) are independently a        hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl        group, an ester group, or an ether group.)

-   -   (in Chemical Formula 101-5, R^(d) is O, S, NH, a substituted or        unsubstituted C1 to C20 alkylene group, C1 to C20 alkylamine        group, or C2 to C20 alkenylamine group.)

The cardo-based binder resin may be, for example prepared by mixing atleast two of a fluorene-containing compound such as 9,9-bis(4-oxiranylmethoxyphenyl)fluorene; an anhydride compound such asbenzenetetracarboxylic acid dianhydride, naphthalenetetracarboxylic aciddianhydride, biphenyltetracarboxylic acid dianhydride,benzophenonetetracarboxylic acid dianhydride, pyromellitic dianhydride,cyclobutanetetracarboxylic acid dianhydride, perylenetetracarboxylicacid dianhydride, tetrahydrofurantetracarboxylic acid dianhydride, andtetrahydrophthalic anhydride; a glycol compound such as ethylene glycol,propylene glycol, and polyethylene glycol; an alcohol compound such asmethanol, ethanol, propanol, n-butanol, cyclohexanol, and benzylalcohol;a solvent-based compound such as propylene glycol methylethylacetate,and N-methylpyrrolidone; a phosphorus compound such astriphenylphosphine; and and an amine or ammonium salt compound such astetramethylammonium chloride, tetraethylammonium bromide,benzyldiethylamine, triethylamine, tributylamine, benzyltriethylammoniumchloride.

When the binder resin is a cardo-based binder resin, the photosensitivecomposition including the same has excellent developability andsensitivity during photo-curing, and thus, has fine pattern-formingcapability.

The binder resin may include a thiol group.

The binder resin may be included in an amount of 1 wt % to 30 wt %, forexample 3 wt % to 20 wt % based on the total amount (total weight) ofthe photosensitive composition. When the binder resin is included withinthe foregoing ranges, excellent sensitivity, developability, resolution,and pattern linearity may be obtained.

(B) Photopolymerizable Monomer

The photopolymerizable monomer may be mono-functional ormulti-functional ester of (meth)acrylic acid including at least oneethylenic unsaturated double bond.

The photopolymerizable monomer has the ethylenic unsaturated doublebond, and thus, may cause suitable or sufficient polymerization duringexposure in a pattern-forming process and form a pattern havingexcellent heat resistance, light resistance, and chemical resistance.

Examples of the photopolymerizable monomer may be ethylene glycoldi(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycoldi(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycoldi(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, bisphenol A di(meth)acrylate, pentaerythritoldi(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritoltetra(meth)acrylate, pentaerythritol hexa(meth)acrylate,dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate,dipentaerythritol penta(meth)acrylate, dipentaerythritolhexa(meth)acrylate, bisphenol A epoxy(meth)acrylate, ethylene glycolmonomethylether (meth)acrylate, trimethylol propane tri(meth)acrylate,tris(meth)acryloyloxyethyl phosphate, novolac epoxy (meth)acrylate, andthe like.

Commercially available examples of the photopolymerizable monomer are asfollows. Examples of the mono-functional ester of (meth)acrylic acid mayinclude Aronix M-101®, M-111®, M-114® (Toagosei Chemistry Industry Co.,Ltd.); KAYARAD TC-110S®, TC-120S® (Nippon Kayaku Co., Ltd.); V-158®,V-2311® (Osaka Organic Chemical Ind., Ltd.), and the like. Examples of adifunctional ester of (meth)acrylic acid may include Aronix M-210®,M-240®, M-6200® (Toagosei Chemistry Industry Co., Ltd.), KAYARAD HDDA®,HX-220®, R-604® (Nippon Kayaku Co., Ltd.), V-260®, V-312®, V-335 HP®(Osaka Organic Chemical Ind., Ltd.), and the like. Examples of atri-functional ester of (meth)acrylic acid may include Aronix M-309®,M-400®, M-405®, M-450®, M-7100®, M-8030®, M-8060® (Toagosei ChemistryIndustry Co., Ltd.), KAYARAD TMPTA®, DPCA-20®, DPCA-30®, DPCA-60®,DPCA-120® (Nippon Kayaku Co., Ltd.), V-295®, V-300®, V-360®, V-GPT®,V-3PA®, V-400® (Osaka Yuki Kayaku Kogyo Co. Ltd.), and the like. Thesemay be used alone or as a mixture of two or more.

The photopolymerizable monomer may be treated with acid anhydride toimprove developability.

The photopolymerizable monomer may be included in an amount of 0.1 wt %to 30 wt %, for example 1 wt % to 20 wt % based on the total amount(total weight) of the photosensitive composition. When thephotopolymerizable monomer is included within the foregoing ranges, thephotopolymerizable monomer is suitably or sufficiently cured duringexposure in a pattern-forming process and thus reliability is improvedand heat resistance, light resistance, chemical resistance, resolutionand a close contacting property of a pattern may be improved.

(C) Photopolymerization Initiator

The photopolymerization initiator may be a generally-used initiator fora photosensitive composition, for example an acetophenone-basedcompound, a benzophenone-based compound, a thioxanthone-based compound,a benzoin-based compound, a triazine-based compound, an oxime-basedcompound, and the like.

Examples of the acetophenone-based compound may be 2,2′-diethoxyacetophenone, 2,2′-dibutoxy acetophenone,2-hydroxy-2-methylpropinophenone, p-t-butyltrichloro acetophenone,p-t-butyldichloro acetophenone, 4-chloro acetophenone,2,2′-dichloro-4-phenoxy acetophenone,2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and thelike.

Examples of the benzophenone-based compound may be benzophenone, benzoylbenzoate, benzoyl methyl benzoate, 4-phenyl benzophenone,hydroxybenzophenone, acrylated benzophenone, 4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone,4,4′-dimethylaminobenzophenone, 4,4′-dichlorobenzophenone,3,3′-dimethyl-2-methoxybenzophenone, and the like.

Examples of the thioxanthone-based compound may be thioxanthone,2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone,2,4-diisopropyl thioxanthone, 2-chlorothioxanthone, and the like.

Examples of the benzoin-based compound may be benzoin, benzoin methylether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutylether, benzyldimethylketal, and the like.

Examples of the triazine-based compound may be2,4,6-trichloro-s-triazine,2-phenyl-4,6-bis(trichloromethyl)-s-triazine,2-(3′,4′-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine,2-(4′-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine,2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine,2-(p-tolyl)-4,6-bis(trichloro methyl)-s-triazine,2-biphenyl-4,6-bis(trichloro methyl)-s-triazine,bis(trichloromethyl)-6-styryl-s-triazine,2-(naphtho1-yl)-4,6-bis(trichloromethyl)-s-triazine,2-(4-methoxynaphtho1-yl)-4,6-bis(trichloromethyl)-s-triazine,2-4-bis(trichloromethyl)-6-piperonyl-s-triazine,2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, and the like.

Examples of the oxime-based compound may be O-acyloxime-based compound,2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octandione,1-(0-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone,O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, and the like. Examplesof the O-acyloxime-based compound may be 1,2-octandione,2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one,1-(4-phenylsulfanyl phenyl)-butane-1,2-dione-2-oxime-O-benzoate,1-(4-phenylsulfanyl phenyl)-octane-1,2-dione-2-oxime-O-benzoate,1-(4-phenylsulfanyl phenyl)-octan-1-oneoxime-O-acetate,1-(4-phenylsulfanyl phenyl)-butan-1-oneoxime-O-acetate, and the like.

The photopolymerization initiator may further include a carbazole-basedcompound, a diketone-based compound, a sulfonium borate-based compound,a diazo-based compound, an imidazole-based compound, a biimidazole-basedcompound, a fluorene-based compound, and the like in addition to theforegoing compounds.

The photopolymerization initiator may be used with a photosensitizercapable of causing a chemical reaction by absorbing light and becomingexcited and then, transferring its energy.

Examples of the photosensitizer may be tetraethylene glycolbis-3-mercapto propionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercapto propionate, and thelike.

The photopolymerization initiator may be included in an amount of 0.1 wt% to 10 wt %, for example 0.1 wt % to 5 wt % based on the total amount(total weight) of photosensitive composition. When thephotopolymerization initiator is included within the foregoing ranges, abalance between sensitivity and developability during exposure isimproved and a pattern having improved resolution without a residualfilm may be obtained.

(E) Solvent

When a photosensitive resin composition includes a photo-conversionmaterial such as a quantum dot and the like instead of a pigment or adye as a color material, a solvent generally used for the photosensitiveresin composition, for example, a polar solvent such as propylene glycolmonomethylether acetate, ethanol, ethylene diglycolmethylethylether, andthe like is difficult to use. However, as described above, since aquantum dot is surface-treated by the compound having one thiol group ata terminal end and/or at the middle of the main chain and an alkoxygroup, a cycloalkyl group, a carboxyl group, or a hydroxy group at theterminal end according to an embodiment, the quantum dot may be used inthe polar solvent, and furthermore, the deterioration problem of aphoto-conversion rate of the quantum dot may be solved or reduced.

For example, the photosensitive composition according to an embodimentmay include, as a solvent alcohols such as methanol, ethanol, and thelike; glycol ethers such as ethylene glycol methylether, ethylene glycolethylether, propylene glycol methylether, and the like; cellosolveacetates such as methyl cellosolve acetate, ethyl cellosolve acetate,diethyl cellosolve acetate, and the like; carbitols such as methylethylcarbitol, diethyl carbitol, diethylene glycol monomethylether,diethylene glycol monoethylether, diethylene glycol dimethylether,diethylene glycol methylethylether, diethylene glycol diethylether, andthe like; propylene glycol alkylether acetates such as propylene glycolmonomethylether acetate, propylene glycol propylether acetate, and thelike; ketones such as methylethylketone, cyclohexanone,4-hydroxy-4-methyl-2-pentanone, methyl-n-propylketone,methyl-n-butylketone, methyl-n-amylketone, 2-heptanone, and the like;saturated aliphatic monocarboxylic acid alkyl esters such as ethylacetate, n-butyl acetate, isobutyl acetate, and the like; lactate esterssuch as methyl lactate, ethyl lactate, and the like; hydroxy acetic acidalkyl esters such as methyl hydroxyacetate, ethyl hydroxyacetate, butylhydroxyacetate, and the like; acetic acid alkoxyalkyl esters such asmethoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate,ethoxymethyl acetate, ethoxyethyl acetate, and the like;3-hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate,ethyl 3-hydroxypropionate, and the like; 3-alkoxypropionic acid alkylesters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate,ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, and the like;2-hydroxypropionic acid alkyl ester such as methyl 2-hydroxypropionate,ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, and the like;2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate,ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl2-ethoxypropionate, and the like; 2-hydroxy-2-methylpropionic acid alkylesters such as methyl 2-hydroxy-2-methylpropionate, ethyl2-hydroxy-2-methylpropionate, and the like; 2-alkoxy-2-methylpropionicacid alkyl esters such as methyl 2-methoxy-2-methylpropionate, ethyl2-ethoxy-2-methylpropionate, and the like; esters such as 2-hydroxyethylpropionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate,methyl 2-hydroxy-3-methylbutanoate, and the like; or ketonate esterssuch as ethyl pyruvate, and the like, and in addition, may beN-methylformamide, N,N-dimethyl formamide, N-methylformanilide,N-methylacetamide, N,N-dimethyl acetamide, N-methylpyrrolidone,dimethylsulfoxide, benzylethylether, dihexylether, acetylacetone,isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol,benzylalcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethylmaleate, γ-butyrolactone, ethylene carbonate, propylene carbonate,phenyl cellosolve acetate, and the like, but is not limited thereto.

For example, the solvent may be desirably glycol ethers such as ethyleneglycol monoethylether, ethylene diglycolmethylethylether, and the like;ethylene glycol alkylether acetates such as ethyl cellosolve acetate,and the like; esters such as 2-hydroxy ethyl propionate, and the like;carbitols such as diethylene glycol monomethylether, and the like;propylene glycol alkylether acetates such as propylene glycolmonomethylether acetate, propylene glycol propylether acetate, and thelike; alcohols such as ethanol, and the like, or a combination thereof.

For example, the solvent may include propylene glycol monomethyletheracetate, dipropylene glycol methylether acetate, ethanol, ethyleneglycoldimethylether, ethylene diglycolmethylethylether, diethyleneglycoldimethylether, 2-butoxyethanol, N-methylpyrrolidine,N-ethylpyrrolidine, propylene carbonate, γ-butyrolactone, or acombination thereof.

The solvent may be included in a balance amount, for example 20 wt % to80 wt %, for example 35 wt % to 80 wt % based on the total amount (totalweight) of the photosensitive composition. When the solvent is withinthe foregoing ranges, the photosensitive composition has suitable orappropriate viscosity and thus may have excellent coating property whencoated in a large area through spin-coating and slit-coating.

(F) Diffusion Agent (or Diffusion Agent Dispersion)

The photosensitive composition according to an embodiment may furtherinclude a diffusion agent.

For example, the diffusion agent may include barium sulfate (BaSO₄),calcium carbonate (CaCO₃), titanium dioxide (TiO₂), zirconia (ZrO₂), ora combination thereof.

The diffusion agent reflects light not absorbed in the abovephoto-conversion material, so that the reflected light may be adsorbedagain in the photo-conversion material. In other words, the diffusionagent increases a dose of the light absorbed in the photo-conversionmaterial and thus photo-conversion efficiency of the photosensitiveresin composition.

The diffusion agent may have an average particle diameter (e.g., D₅₀) of150 nm to 250 nm, for example, 180 nm to 230 nm. When the diffusionagent has an average particle diameter within the foregoing ranges, muchmore excellent light scattering effects may be obtained, andphoto-conversion efficiency may be increased.

The diffusion agent may be included in an amount of 0.1 wt % to 20 wt %,for example 1 wt % to 15 wt % based on a total solid amount of thephotosensitive resin composition. When the diffusion agent is includedin an amount of less than 0.1 wt % based on a total weight of thephotosensitive composition, improvement of photo-conversion efficiencymay be difficult to obtain, while when the scatterer is included in anamount of greater than 20 wt %, pattern characteristics may bedeteriorated.

(G) Other Additives

The photosensitive resin composition according to an embodiment mayfurther include a polymerization inhibitor including ahydroquinone-based compound, a catechol-based compound, or a combinationthereof. The photosensitive resin composition according to an embodimentmay inhibit or reduce cross-linking at room temperature during exposureafter coating the photosensitive composition by further including thehydroquinone-based compound, the catechol-based compound, or thecombination thereof.

For example, the hydroquinone-based compound, the catechol-basedcompound, or the combination thereof may be hydroquinone, methylhydroquinone, methoxyhydroquinone, t-butyl hydroquinone, 2,5-di-t-butylhydroquinone, 2,5-bis(1,1-dimethylbutyl) hydroquinone, 2,5-bis(1,1,3,3-tetramethylbutyl) hydroquinone, catechol, t-butyl catechol,4-methoxyphenol, pyrogallol, 2,6-di-t-butyl-4-methylphenol, 2-naphthol,tris(N-hydroxy-N-nitrosophenylaminato-O,O′)aluminum, or a combinationthereof, but are not limited thereto.

The hydroquinone-based compound, catechol-based compound or combinationthereof may be used in a form of dispersion, and the polymerizationinhibitor in a form of the dispersion may be included in an amount of0.001 wt % to 1 wt %, for example 0.01 wt % to 0.1 wt % based on thetotal amount (total weight) of the photosensitive composition. When thepolymerization inhibitor is included within the foregoing ranges,passage of time at room temperature may be solved or reduced andconcurrently (e.g., simultaneously), sensitivity deterioration andsurface delamination phenomenon may be inhibited or reduced.

In addition, the photosensitive resin composition according to anembodiment may further include malonic acid; 3-amino-1,2-propanediol; asilane-based coupling agent; a leveling agent; a fluorine-basedsurfactant; or a combination thereof in order to improve heat resistanceand reliability.

For example, the photosensitive composition may further include asilane-based coupling agent having a reactive substituent such as avinyl group, a carboxyl group, a methacryloxy group, an isocyanategroup, an epoxy group and the like in order to improve close contactingproperties with a substrate.

Examples of the silane-based coupling agent may be trimethoxysilylbenzoic acid, γ-methacryl oxypropyl trimethoxysilane, vinyltriacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyltriethoxysilane, γ-glycidoxy propyl trimethoxysilane,β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like, and thesemay be used alone or in a mixture of two or more.

The silane-based coupling agent may be used in an amount of 0.01 partsby weight to 10 parts by weight based on 100 parts by weight of thephotosensitive composition. When the silane-based coupling agent isincluded within the foregoing ranges, close contacting properties,storage capability, and the like are improved.

The photosensitive composition may further include a surfactant, forexample a fluorine-based surfactant as needed or desired in order toimprove coating properties and inhibit or reduce generation of spots(e.g., improve leveling performance).

The fluorine-based surfactant may have a low weight average molecularweight of 4,000 g/mol to 10,000 g/mol, and, for example, 6,000 g/mol to10,000 g/mol. In addition, the fluorine-based surfactant may have asurface tension of 18 mN/m to 23 mN/m (measured in a 0.1% polyethyleneglycol monomethylether acetate (PGMEA) solution). When thefluorine-based surfactant has a weight average molecular weight and asurface tension within the foregoing ranges, leveling performance may befurther improved, and excellent characteristics may be provided whenslit coating as high speed coating is applied since film defects may beless generated by preventing (or reducing) a spot generation during thehigh speed coating and suppressing (or reducing) the generation of vaporgeneration.

Examples of the fluorine-based surfactant may be, BM-1000®, and BM-1100®(BM Chemie Inc.); MEGAFACE F 142D®, F 172®, F 173®, and F 183® DainipponInk Kagaku Kogyo Co., Ltd.); FULORAD FC-135®, FULORAD FC-170C®, FULORADFC-430®, and FULORAD FC-431® (Sumitomo 3M Co., Ltd.); SURFLON S-112®,SURFLON S-113®, SURFLON S-131®, SURFLON S-141®, and SURFLON S-145®(ASAHI Glass Co., Ltd.); and SH-28PA®, SH-190®, SH-193®, SZ-6032®, andSF-8428®, and the like (Toray Silicone Co., Ltd.); F-482, F-484, F-478,F-554 and the like of DIC Co., Ltd.

The surfactant may further include a silicone-based surfactant inaddition to the fluorine-based surfactant. Examples of thesilicone-based surfactant may be TSF400, TSF401, TSF410, TSF4440, andthe like of Toshiba silicone Co., Ltd., but is not limited thereto.

The surfactant may be included in an amount of 0.01 parts by weight to 5parts by weight, for example 0.1 parts by weight to 2 parts by weightbased on 100 parts by weight of the photosensitive composition. When thesurfactant is included within the foregoing ranges, foreign materialsare less produced after the development.

In addition, the photosensitive composition according to an embodimentmay further include other additives such as an antioxidant, astabilizer, and the like in a set or predetermined amount, unless theresultant properties are deteriorated.

Another embodiment provides a curable composition including (A′) aresin; (B′) a quantum dot surface-modified with the compound representedby Chemical Formula 1 or Chemical Formula 2; and (C′) a solvent.

Since the curable composition according to another embodiment does notrequire an additional process such as an exposure, a development,curing, or the like, the quantum efficiency deterioration of the quantumdot in the curable composition may be minimized or reduced, andfurthermore, deterioration of a photo-conversion rate may be minimizedor reduced by surface-modifying the quantum dot with the compoundrepresented by Chemical Formula 1 or 2. For example, a different curablecomposition according to another embodiment is very suitable orappropriate for an inkjet process, and thus, does not have (orsubstantially does not have) a problem according to an existinglithography problem, for example, a problem of rarely forming a finepattern due to lack of light source energy.

Hereinafter, each component is described in more detail.

(A′) Resin

The (A′) resin may include a binder resin and a reactive unsaturatedcompound.

The binder resin may include an acryl-based resin, an epoxy resin, or acombination thereof.

The acryl-based resin is a copolymer of a first ethylenic unsaturatedmonomer and a second ethylenic unsaturated monomer that iscopolymerizable therewith, and may be a resin including at least oneacryl-based repeating unit.

The first ethylenic unsaturated monomer is an ethylenic unsaturatedmonomer including at least one carboxyl group and examples of themonomer include acrylic acid, methacrylic acid, maleic acid, itaconicacid, fumaric acid, or a combination thereof.

The first ethylenic unsaturated monomer may be included in an amount of5 to 50 wt %, for example, 10 to 40 wt % based on the total amount(total weight) of the acryl-based binder resin.

The second ethylenic unsaturated monomer may be an aromatic vinylcompound such as styrene, α-methylstyrene, vinyl toluene,vinylbenzylmethylether and the like; an unsaturated carboxylate estercompound such as methyl(meth)acrylate, ethyl(meth)acrylate,butyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, benzyl(meth)acrylate, cyclohexyl(meth)acrylate,phenyl(meth)acrylate, and the like; an unsaturated amino alkylcarboxylate ester compound such as 2-aminoethyl(meth)acrylate,2-dimethylaminoethyl(meth)acrylate, and the like; a carboxylic acidvinyl ester compound such as vinyl acetate, vinyl benzoate, and thelike; an unsaturated glycidyl carboxylate ester compound such asglycidyl(meth)acrylate, and the like; a vinyl cyanide compound such as(meth)acrylonitrile and the like; an unsaturated amide compound such as(meth)acrylamide, and the like; and the like, and may be used alone oras a mixture of two or more.

Examples of the acryl-based binder resin may be apolybenzylmethacrylate, (meth)acrylic acid/benzylmethacrylate copolymer,a (meth)acrylic acid/benzylmethacrylate/styrene copolymer, a(meth)acrylic acid/benzylmethacrylate/2-hydroxyethylmethacrylatecopolymer, a (meth)acrylicacid/benzylmethacrylate/styrene/2-hydroxyethylmethacrylate copolymer,and the like, but are not limited thereto, and may be used alone or as amixture of two or more.

A weight average molecular weight of the acryl-based resin may be 5,000g/mol to 15,000 g/mol. When the acryl-based resin has a weight averagemolecular weight within the foregoing range, close-contacting propertiesto a substrate, physical and chemical properties are improved, and aviscosity is suitable or appropriate.

An acid value of the acryl-based resin may be 80 mg KOH/g to 130mgKOH/g. When the acryl-based resin has an acid value within theforegoing range, excellent resolution of a pixel may be obtained.

The epoxy resin may be a thermally polymerizable monomer or oligomer,and may include a compound having a carbon-carbon unsaturated bond and acarbon-carbon cyclic bond.

For example, the epoxy resin may be at least two kinds of epoxy resinsessentially including a compound represented by Chemical Formula 5-1 anda compound represented by Chemical Formula 5-2.

-   -   (in Chemical Formula 5-1 and Chemical Formula 5-2,    -   R² to R⁸ are independently a hydrogen atom, a halogen atom, or        C1 to C5 alkyl group, and    -   p is an integer in a range of 0 to 25.)

The epoxy resin may further include a bisphenol A epoxy resin, abisphenol F epoxy resin, a phenol novolac epoxy resin, a cyclicaliphatic epoxy resin, and an aliphatic polyglycidyl ether in additionto the compounds of Chemical Formula 5-1 and Chemical Formula 5-2.

As commercially available examples of such compounds, a bisphenyl epoxyresin represented by Chemical Formula 5-1 may be YX4000, YX4000H,YL6121H, YL6640, or YL6677 of Yuka Shell Epoxy Co.; a cresol novolacepoxy resin represented by Chemical Formula 5-2 may be EOCN-102,EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, or EOCN-1027 of NipponKayaku Co. Ltd. and EPIKOTE 180S75 of Yuka Shell Epoxy Co.; a bisphenolA epoxy resin may be EPIKOTE 1001, 1002, 1003, 1004, 1007, 1009, 1010and 828 of Yuka Shell Epoxy Co.; a bisphenol F epoxy resin may beEPIKOTE 807 and 834 of Yuka Shell Epoxy Co.; a phenol novolac epoxyresin may be EPIKOTE 152, 154, or 157H65 of Yuka Shell Epoxy Co. andEPPN 201, 202 of Nippon Kayaku Co. Ltd.; a cyclic aliphatic epoxy resinmay be CY175, CY177 and CY179 of CIBA-GEIGY A.G Corp., ERL-4234,ERL-4299, ERL-4221 and ERL-4206 of U.C.C., Showdyne 509 of Showa DenkoK.K., Araldite CY-182 of CIBA-GEIGY A.G Corp., CY-192 and CY-184,Dainippon Ink & Chemicals Inc. EPICLON 200 and 400, EPIKOTE 871, 872 ofYuka Shell Epoxy Co. and EP1032H60, ED-5661 and ED-5662 of CelaneseCoating Corporation; an aliphatic polyglycidylether may be EPIKOTE 190Pand 191P of Yuka Shell Epoxy Co., EPOLITE 100MF of Kyoeisha Yushi KagakuKogyo Co., Ltd., EPIOL TMP of Nihon Yushi K. K., and the like.

The reactive unsaturated compound may be used with a generally-usedmonomer or oligomer in an existing thermosetting composition.

The reactive unsaturated compound may be for example one or moreselected from ethylene glycoldiacrylate, triethylene glycoldiacrylate,1,4-butanedioldiacrylate, 1,6-hexanedioldiacrylate,neopentylglycoldiacrylate, pentaerythritoldiacrylate,pentaerythritoltriacrylate, dipentaerythritoldiacrylate,dipentaerythritoltriacrylate, dipentaerythritolpentaacrylate,pentaerythritolhexaacrylate, bisphenol A diacrylate,trimethylolpropanetriacrylate, novolacepoxyacrylate, ethyleneglycoldimethacrylate, diethylene glycoldimethacrylate, triethyleneglycoldimethacrylate, propylene glycoldimethacrylate,1,4-butanedioldimethacrylate, and 1,6-hexanedioldimethacrylate.

The resin may be included in an amount of 1 wt % to 40 wt %, for example5 wt % to 30 wt % based on the total amount (total weight) of thecurable composition. When the resin is included within the foregoingranges, patterns formed by inkjet printing of the same may exhibitimproved reliability such as heat resistance, chemical resistance, filmstrengths, and physical characteristics.

(C′) Solvent

When a curable composition includes a photo-conversion material such asa quantum dot and the like instead of a pigment or a dye as a colormaterial, a solvent generally used for the curable composition, forexample, a polar solvent such as propylene glycol monomethyletheracetate, ethanol, ethylene diglycolmethylethylether, and the like isdifficult to use. However, as described above, since the surface of aquantum dot is modified by the compound represented by Chemical Formula1 or 2 according to an embodiment, the quantum dot may be used in thepolar solvent, and furthermore, the deterioration problem of aphoto-conversion rate of the quantum dot may be solved or reduced.

In other words, the curable composition according to an embodiment mayuse a solvent including the photosensitive composition.

The solvent may be included in a balance amount, for example 20 wt % to80 wt %, for example 35 wt % to 80 wt % based on the total amount (totalweight) of the curable composition. When the solvent is within theforegoing ranges, the curable composition has suitable or appropriateviscosity, and thus, may have excellent coating property when coated ina large area through spin-coating and slit-coating.

Diffusion Agent (or Diffusion Agent Dispersion)

The curable composition according to an embodiment may further include adiffusion agent. The diffusion agent is the same as described hereinabove.

Polymerization Initiator

The curable composition may further include a polymerization initiatorin order to improve the strength or integrity of the resultant patterns.

The polymerization initiator may be a cation initiator. The cationinitiator initiates a polymerization of the resin, and may be anysuitable cation initiator available in the art, for example, sulfoniumsalts such as triallylsulfoniumhexafluorophosphate,triarylsulfoniumhexafluoroantimonate, and the like; iodonium salts suchas diaryliodonium hexafluorophosphate, diphenyliodoniumhexafluoroantimonate, bis(dodecylphenyl)iodoniumtetrakis(pentafluorophenyl)borate, iodonium[4-(4-methylphenyl-2-methylpropyl)phenyl]hexafluorophosphate, and thelike; phosphonium salts such as tetrafluorophosphoniumhexafluorophosphate; pyridinium salts, and the like.

When the curable composition further includes the polymerizationinitiator, the polymerization initiator may be included in an amount of0.01 parts by weight to 10 parts by weight, for example 0.05 parts byweight to 5 parts by weight based on 100 parts by weight of the curablecomposition. When the polymerization initiator is included in an amountof less than 0.01 parts by weight, a curing rate of the resin is so slowthat strength improvement of patterns may be unsuitable or insufficient,while when it is greater than 10 parts by weight, the curing rate of theresin is so fast that storage stability may be unstable and viscositymay be continuously increased and thus discharge performance may bedeteriorated.

Other Additives

The curable composition according to an embodiment may further include apolymerization inhibitor including a hydroquinone-based compound, acatechol-based compound, or a combination thereof. The curablecomposition according to an embodiment may inhibit or reducecross-linking at room temperature during exposure after coating thecurable composition by further including the hydroquinone-basedcompound, the catechol-based compound, or a combination thereof.

For example, the hydroquinone-based compound, the catechol-basedcompound, or the combination thereof may be hydroquinone, methylhydroquinone, methoxyhydroquinone, t-butyl hydroquinone, 2,5-di-t-butylhydroquinone, 2,5-bis(1,1-dimethylbutyl) hydroquinone, 2,5-bis(1,1,3,3-tetramethylbutyl) hydroquinone, catechol, t-butyl catechol,4-methoxyphenol, pyrogallol, 2,6-di-t-butyl-4-methylphenol, 2-naphthol,tris(N-hydroxy-N-nitrosophenylaminato-O,O′)aluminum, or a combinationthereof, but are not limited thereto.

The hydroquinone-based compound, catechol-based compound or combinationthereof may be used in a form of dispersion, and the polymerizationinhibitor in a form of the dispersion may be included in an amount of0.001 wt % to 1 wt %, for example 0.01 wt % to 0.1 wt % based on thetotal amount (total weight) of the curable composition. When thepolymerization inhibitor is included within the foregoing ranges,passage of time at room temperature may be solved or reduced andconcurrently (e.g., simultaneously), sensitivity deterioration andsurface delamination phenomenon may be inhibited or reduced.

In addition, the curable composition according to an embodiment mayfurther include malonic acid; 3-amino-1,2-propanediol; a silane-basedcoupling agent; a leveling agent; a fluorine-based surfactant; or acombination thereof in order to improve heat resistance and reliability.

For example, the curable composition may further include a silane-basedcoupling agent having a reactive substituent such as a vinyl group, acarboxyl group, a methacryloxy group, an isocyanate group, an epoxygroup and the like in order to improve close contacting properties witha substrate.

Examples of the silane-based coupling agent may be trimethoxysilylbenzoic acid, γ-methacryl oxypropyl trimethoxysilane, vinyltriacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyltriethoxysilane, γ-glycidoxy propyl trimethoxysilane,β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like, and thesemay be used alone or in a mixture of two or more.

The silane-based coupling agent may be used in an amount of 0.01 partsby weight to 10 parts by weight based on 100 parts by weight of thecurable composition. When the silane-based coupling agent is includedwithin the foregoing range, close contacting properties, storagecapability, and the like are improved.

The curable composition may further include a surfactant, for example afluorine-based surfactant as desired or needed in order to improvecoating properties and inhibit or reduce generation of spots (e.g.,improve leveling performance).

The fluorine-based surfactant may have a low weight average molecularweight of 4,000 g/mol to 10,000 g/mol, and, for example, 6,000 g/mol to10,000 g/mol. In addition, the fluorine-based surfactant may have asurface tension of 18 mN/m to 23 mN/m (measured in a 0.1% polyethyleneglycol monomethylether acetate (PGMEA) solution). When thefluorine-based surfactant has a weight average molecular weight and asurface tension within the foregoing ranges, leveling performance may befurther improved, and excellent characteristics may be provided whenslit coating as high speed coating is applied since film defects may beless generated by preventing (or reducing) a spot generation during thehigh speed coating and suppressing (or reducing) the generation ofvapor.

Examples of the fluorine-based surfactant may be, BM-1000®, and BM-1100®(BM Chemie Inc.); MEGAFACE F 142D®, F 172®, F 173®, and F 183® DainipponInk Kagaku Kogyo Co., Ltd.); FULORAD FC-135®, FULORAD FC-170C®, FULORADFC-430®, and FULORAD FC-431® (Sumitomo 3M Co., Ltd.); SURFLON S-112®,SURFLON S-113®, SURFLON S-131®, SURFLON S-141®, and SURFLON S-145®(ASAHI Glass Co., Ltd.); and SH-28PA®, SH-190®, SH-193®, SZ-6032®, andSF-8428®, and the like (Toray Silicone Co., Ltd.); F-482, F-484, F-478,F-554 and the like of DIC Co., Ltd.

The surfactant may further include a silicone-based surfactant inaddition to the fluorine-based surfactant. Examples of thesilicone-based surfactant may be TSF400, TSF401, TSF410, TSF4440, andthe like of Toshiba silicone Co., Ltd., but is not limited thereto.

The surfactant may be included in an amount of 0.01 parts by weight to 5parts by weight, for example 0.1 parts by weight to 2 parts by weightbased on 100 parts by weight of the photosensitive composition. When thesurfactant is included within the foregoing ranges, foreign materialsare less produced after the development.

In addition, the curable composition according to an embodiment mayfurther include other additives such as an antioxidant, a stabilizer,and the like in a set or predetermined amount, unless properties aredeteriorated.

Another embodiment provides a photosensitive resin film manufacturedusing the photosensitive resin composition and a color filter includingthe photosensitive resin film. The color filter may be manufactured asfollows.

(1) Coating and Film Formation

The photosensitive resin composition is coated to have a desiredthickness, for example, a thickness in a range of 2 μm to 10 μm, on asubstrate which undergoes a set or predetermined pretreatment, using aspin or slit coating method, a roll coating method, a screen-printingmethod, an applicator method, and the like. Then, the coated substrateis heated at a temperature in a range of 70° C. to 90° C. for 1 minuteto 10 minutes to remove a solvent.

(2) Exposure

The resultant film is radiated by an active ray such as UV ray having awavelength of 190 nm to 450 nm, for example 200 nm to 500 nm afterputting a mask with a set or predetermined shape to form a desiredpattern. The radiation is performed by using a light source such as amercury lamp with a low pressure, a high pressure, or an ultrahighpressure, a metal halide lamp, an argon gas laser, and the like. An Xray, an electron beam, and the like may be also used as desired orneeded.

Exposure process uses, for example, a light dose of 500 mJ/cm² or less(with a 365 nm sensor) when a high pressure mercury lamp is used.However, the light dose may vary depending on kinds of each component ofthe black photosensitive resin composition, its combination ratio, and adry film thickness.

(3) Development

After the exposure process, an alkali aqueous solution is used todevelop the exposed film by dissolving and removing a set or unnecessarypart except the exposed part, forming an image pattern. In other words,when the alkali developing solution is used for the development, anon-exposed region is dissolved, and an image color filter pattern isformed.

(4) Post-Treatment

The developed image pattern may be heated again or radiated by an activeray and the like for curing, in order to accomplish excellent quality interms of heat resistance, photo resistance, close contacting properties,crack-resistance, chemical resistance, high strength, storage stability,and the like.

Another embodiment provides a method of manufacturing a pixel for acolor filter using the curable composition and a color filter includingthe pixel manufactured with the manufacturing method.

The method of manufacturing the pixel for the color filter may includecoating the curable composition on a substrate with an inkjet sprayingmethod to form a pattern (S1); and curing the pattern (S2).

(S1) Formation of Pattern

The curable composition may be coated to be 0.5 to 3.0 μm thick on asubstrate utilizing an inkjet spraying method. The inkjet sprayingmethod may form a pattern by spraying a single color, and thus,repeating the spraying as many times as the desired or needed number ofcolors, but the pattern may be formed by concurrently (e.g.,simultaneously) spraying the desired or needed number of colors.

(S2) Curing

The obtained pattern is cured to obtain a pixel. Herein, the curing maybe thermal curing. The thermal curing may be performed at a temperaturegreater than or equal to 160° C., for example, in a range of 160° C. to300° C., or in a range of 200° C. to 250° C.

Another embodiment provides a method of manufacturing thesurface-modified quantum dot. The method of manufacturing thesurface-modified quantum dot includes dispersing quantum dotssurface-modified with oleic acid in a nonpolar solvent; adding acompound having a thiol group at one terminal end and an alkoxy group, acycloalkyl group, a carboxyl group, or a hydroxy group at the otherterminal end, and a metal salt thereto and stirring the same; and beingsubject to centrifugation of the stirred solution (e.g., centrifugingthe stirred solution) to separate a supernatant and lower liquidfollowed by drying the lower liquid.

When the surface of the quantum dot having a core/shell structureincludes (or consists of) a bond of a metal cation and anion or an atomhaving a δ(−) charge (e.g., Zn and S as for a CdSe/ZnS quantum dot), anatom including (or consisting of) an outermost layer forms a danglingbond due to electrons/holes not participated in the bonding. Thisdangling bond works as a quenching site of excited electrons and thusmainly deteriorates luminous efficiency. Herein, when the surface of thequantum dot is capped with an anion or a cation, a deep/shallow trapstate of a bandgap is effectively passivated, and resultantly, theluminous efficiency deterioration may be reduced.

In other words, a cation in the metal salt compound is coordinated withan atom including (or consisting of) an outermost layer of the quantumdot (a primary metal ion passivation), and thus, may induce or deducepassivation of a thiol-based ligand in a more amount (a secondary thiolligand passivation). Herein, before the coordination bond of the cationin the metal salt compound, the outermost layer of the quantum dot hasbeen already passivated by the thiol-based ligand.

The metal salt compound may include a zinc cation, an indium cation, alead cation, a cadmium cation, or a combination thereof.

For example, the metal salt compound may be ZnCl₂ or InCl₃.

In addition, the stirring may be performed at a temperature of 60° C. to70° C. When the stirring is performed at 60° C. to 70° C. rather thanwhen the stirring is performed at room temperature of 20° C., a ligandexchange reaction (substituting a thiol-based ligand for an oleic acidligand) rate is constantly (or substantially constantly) maintainedregardless of an amount of the salt compound, and thus, excellentpatternability may be obtained.

The surface-modified quantum dot is the same as described above.

The quantum dot powder manufactured by embodiments of the method may bedispersed in a polar solvent such as PGMEA and the like to prepare thephotosensitive resin composition.

Hereinafter, embodiments of the present disclosure are illustrated inmore detail with reference to examples. These examples, however, are notin any sense to be interpreted as limiting the scope of the presentdisclosure.

(Preparation of Quantum Dot Dispersion Solution) Preparation Example 1

0.33 g of a compound represented by Chemical Formula 1-1 and 23.3 mg ofZnCl₂ were added to 3.33 g of an InP/ZeSe/ZnS-oleate ligand quantum dotsolution dispersed in cyclohexane (fluorescence λ_(em)=542 nm, FWHM=37nm, Green QD, Hansol Chemical Co., Ltd.) (a solid content: 30%), and themixture was stirred at room temperature (20° C.) for 12 hours. After 12hours, the resultant was chemically precipitated by using a centrifuge(7000 rpm, 10 min) to separate and remove an upper solution therefrom.The rest thereof was dried by using a vacuum oven at room temperature(20° C.) for 3 hours to separate quantum dot powder ligand-exchangedwith a compound represented by Chemical Formula 1-1 and dispersed in2.33 g of PGMEA to prepare a quantum dot dispersion solution having asolid content of 30%.

Preparation Example 2

A quantum dot dispersion solution having a solid content of 30% wasprepared according to substantially the same method as PreparationExample 1 except for using ZnCl₂ in an amount of 11.65 mg instead of23.3 mg.

Preparation Example 3

A quantum dot dispersion solution having a solid content of 30% wasprepared according to substantially the same method as PreparationExample 1 except for using ZnCl₂ in an amount of 5.82 mg instead of 23.3mg.

Preparation Example 4

A quantum dot dispersion solution having a solid content of 30% wasprepared according to substantially the same method as PreparationExample 1 except for using ZnCl₂ in an amount of 2.91 mg instead of 23.3mg.

Preparation Example 5

A quantum dot dispersion solution having a solid content of 30% wasprepared according to substantially the same method as PreparationExample 1 except for not using ZnCl₂.

Preparation Example 6

A quantum dot dispersion solution having a solid content of 30% wasprepared according to substantially the same method as PreparationExample 5 except for using a compound represented by Chemical Formula1-2 instead of the compound represented by Chemical Formula 1-1.

Preparation Example 1-1

A quantum dot dispersion solution having a solid content of 30% wasprepared according to substantially the same method as PreparationExample 1 except for changing the temperature for the stirring from roomtemperature to 65° C.

Preparation Example 2-1

A quantum dot dispersion solution having a solid content of 30% wasprepared according to substantially the same method as PreparationExample 2 except for changing the temperature for the stirring from roomtemperature to 65° C.

Preparation Example 3-1

A quantum dot dispersion solution having a solid content of 30% wasprepared according to substantially the same method as PreparationExample 3 except for changing the temperature for the stirring from roomtemperature to 65° C.

Preparation Example 4-1

A quantum dot dispersion solution having a solid content of 30% wasprepared according to substantially the same method as PreparationExample 4 except for changing the temperature for the stirring from roomtemperature to 65° C.

Preparation Example 5-1

A quantum dot dispersion solution having a solid content of 30% wasprepared according to substantially the same method as PreparationExample 5 except for changing the temperature for the stirring from roomtemperature to 65° C.

Preparation Example 6-1

A quantum dot dispersion solution having a solid content of 30% wasprepared according to substantially the same method as PreparationExample 6 except for changing the temperature for the stirring from roomtemperature to 65° C.

Preparation Example 7

A quantum dot dispersion solution having a solid content of 30% wasprepared according to substantially the same method as PreparationExample 1-1 except for using a compound represented by Chemical Formula1-2 instead of the compound represented by Chemical Formula 1-1.

Preparation Example 8

A quantum dot dispersion solution having a solid content of 30% wasprepared according to substantially the same method as PreparationExample 1-1 except for using a compound represented by Chemical Formula1-7 instead of the compound represented by Chemical Formula 1-1.

Preparation Example 9

A quantum dot dispersion solution having a solid content of 30% wasprepared according to substantially the same method as PreparationExample 1-1 except for using a compound represented by Chemical FormulaA-4 instead of the compound represented by Chemical Formula 1-1.

Preparation Example 10

A quantum dot dispersion solution having a solid content of 30% wasprepared according to substantially the same method as PreparationExample 1-1 except for using a compound represented by Chemical Formula1-3 instead of the compound represented by Chemical Formula 1-1.

-   -   (in Chemical Formula 1-3, m is an integer of 3.)

Preparation Example 11

A quantum dot dispersion solution having a solid content of 30% wasprepared according to substantially the same method as PreparationExample 1-1 except for using a compound represented by Chemical Formula1-6 instead of the compound represented by Chemical Formula 1-1.

-   -   (in Chemical Formula 1-6, m is an integer of 3.)

Preparation Example 12

A quantum dot dispersion solution having a solid content of 30% wasprepared according to substantially the same method as PreparationExample 1-1 except for using a compound represented by Chemical Formula1-4 instead of the compound represented by Chemical Formula 1-1.

-   -   (in Chemical Formula 1-4, m is an integer of 3.)

Preparation Example 13

A quantum dot dispersion solution having a solid content of 30% wasprepared according to substantially the same method as PreparationExample 1-1 except for using a compound represented by Chemical Formula1-5 instead of the compound represented by Chemical Formula 1-1.

Preparation Example 14

A quantum dot dispersion solution having a solid content of 30% wasprepared according to substantially the same method as PreparationExample 1-1 except for using a compound represented by Chemical Formula2-1 instead of the compound represented by Chemical Formula 1-1.

Comparative Preparation Example 1

A quantum dot dispersion solution having a solid content of 30% wasprepared according to substantially the same method as PreparationExample 1 except for using cyclohexylacetate instead of PGMEA.

Comparative Preparation Example 2

A quantum dot dispersion solution having a solid content of 30% wasprepared according to substantially the same method as PreparationExample 1-1 except for using PE-TSA represented by the followingchemical formula instead of the compound represented by Chemical Formula1-1.

Comparative Preparation Example 3

A quantum dot dispersion solution having a solid content of 30% wasprepared according to substantially the same method as PreparationExample 1-1 except for using PE-TSA represented by Chemical Formula C-1instead of the compound represented by Chemical Formula 1-1.

Comparative Preparation Example 4

A quantum dot dispersion solution having a solid content of 30% wasprepared according to substantially the same method as PreparationExample 1-1 except for using PE-TSA represented by Chemical Formula C-2instead of the compound represented by Chemical Formula 1-1.

Evaluation 1: Dispersibility

A particle size of quantum dots in each quantum dot dispersion solutionaccording to Preparation Example 1 and Comparative Preparation Example 1was respectively three times measured by a particle size analyzer, andthe results are shown in Table 1.

TABLE 1 Comparative Preparation Preparation Example 1 Example 1 Particlesize (nm) 15.8 16.0

Referring to Table 1, the particle diameter of quantum dots in thedispersion solutions according to Preparation Example 1 and ComparativePreparation Example 1 were substantially the same (approximately 16 nm),and accordingly, the quantum dots surface-modified with the compoundrepresented by Chemical Formula 1-1 turned out to have substantiallyequivalent dispersibility to an existing level in a polar solvent suchas PGMEA.

Evaluation 2: Patternability

The dispersion solutions according to Preparation Examples 1 to 6respectively correspond to {circle around (1)} to {circle around (6)} ofFIG. 1 , the dispersion solutions according to Preparation Examples 1-1to 6-1 respectively correspond to {circle around (1)} to {circle around(6)} of FIG. 2 , and referring to FIGS. 1-2 , as a smaller amount ofZnCl₂ was dispersed at room temperature, a ligand exchange reaction ratebecame slower, but when ZnCl₂ was dispersed at 65° C., a chemicalprecipitate was separated at a constant rate regardless of the amount ofZnCl₂, and accordingly, 65° C. turned out to be suitable forpatternability to room temperature as a temperature for dispersion. Inaddition, Zn of ZnCl₂ turned out to function as a catalyst in the ligandexchange reaction.

(Preparation of Photosensitive Composition)

Each photosensitive resin composition according to Examples 1 to 9 andComparative Examples 1 to 4 was prepared to have a composition shown inTables 2 and 3 by using the following components.

A photopolymerization initiator was dissolved in a solvent, and thesolution is suitably or sufficiently stirred at room temperature for 2hours. Subsequently, an acryl-based binder resin along with the quantumdots (Preparation Example 1 and Comparative Preparation Example 1) and adispersing agent (TEGO D685 made by EVONIK) was added thereto, and theobtained mixture was stirred again at room temperature for 2 hours.Then, a diffusion agent and a fluorine-based surfactant were addedthereto, a mixture obtained therefrom was stirred at room temperaturefor one hour, and a product therefrom was three times filtered to removeimpurities to prepare photosensitive resin compositions. (The dispersingagent is added in an amount of 15 wt % relative to a solid content ofthe quantum dots)

-   -   (A) Binder Resin    -   Acryl-based binder resin (TB04, TACOMA)    -   (B) Photopolymerizable Monomer    -   Tricyclodecane dimethanol diacrylate (TCI)    -   (C) Photopolymerization Initiator    -   PBG 305 (Tronly)    -   Quantum Dot    -   (D-1) Quantum dot dispersion solution of Preparation Example 1    -   (D-2) Quantum dot dispersion solution of Preparation Example 7    -   (D-3) Quantum dot dispersion solution of Preparation Example 8    -   (D-4) Quantum dot dispersion solution of Preparation Example 9    -   (D-5) Quantum dot dispersion solution of Preparation Example 10    -   (D-6) Quantum dot dispersion solution of Preparation Example 11    -   (D-7) Quantum dot dispersion solution of Preparation Example 12    -   (D-8) Quantum dot dispersion solution of Preparation Example 13    -   (D-9) Quantum dot dispersion solution of Preparation Example 14    -   (D-10) Quantum dot dispersion solution of Comparative        Preparation Example 1    -   (D-11) Quantum dot dispersion solution of Comparative        Preparation Example 2    -   (D-12) Quantum dot dispersion solution of Comparative        Preparation Example 3    -   (D-13) Quantum dot dispersion solution of Comparative        Preparation Example 4    -   (E) Solvent    -   Propylene Glycol Monomethylether Acetate (PGMEA, Sigma-Aldrich        Corporation)    -   (F) Diffusion Agent    -   Titanium dioxide dispersion (TiO2 solid: 20 wt %, Average        particle diameter: 200 nm, Ditto Technology)    -   (G) Other Additives    -   Leveling agent (F-554, DIG Go., Ltd.)

TABLE 2 (unit: wt %) Example 1 Example 2 Example 3 Example 4 Example 5Example 6 Example 7 (A) Binder resin 9.8 9.8 9.8 9.8 9.8 9.8 9.8 (B)Photopolymerizable monomer 1.6 1.6 1.6 1.6 1.6 1.6 1.6 (C)Photopolymerization initiator 0.1 0.1 0.1 0.1 0.1 0.1 0.1 (D) QuantumD-1 13 — — — — — — dot D-2 — 13 — — — — — D-3 — — 13 — — — — D-4 — — —13 — — — D-5 — — — — 13 — — D-6 — — — — — 13 — D-7 — — — — — — 13 (F)Solvent 60.4 60.4 60.4 60.4 60.4 60.4 60.4 (F) Diffusion agent 12.6 12.612.6 12.6 12.6 12.6 12.6 (G) Other additive 2.5 2.5 2.5 2.5 2.5 2.5 2.5

TABLE 3 (unit: wt %) Comparative Comparative Comparative ComparativeExample 8 Example 9 Example 1 Example 2 Example 3 Example 4 (A) Binderresin 9.8 9.8 9.8 9.8 9.8 9.8 (B) Photopolymerizable monomer 1.6 1.6 1.61.6 1.6 1.6 (C) Photopolymerization initiator 0.1 0.1 0.1 0.1 0.1 0.1(D) Quantum D-8 13 — — — — — dot D-9 — 13 — — — — D-10 — — 13 — — — D-11— — — 13 — — D-12 — — — — 13 — D-13 — — — — — 13 (F) Solvent 60.4 60.460.4 60.4 60.4 60.4 (F) Diffusion agent 12.6 12.6 12.6 12.6 12.6 12.6(G) Other additives 2.5 2.5 2.5 2.5 2.5 2.5

Evaluation 3: Photo-Conversion Rate and Photo Maintenance Rate ofQuantum Dot

The photosensitive resin compositions according to Examples 1 to 9 andComparative Examples 1 to 4 were respectively coated into a 5 μm-thicksingle film on a glass substrate by using a spin-coater (150 rpm,Opticoat MS-A150, Mikasa Co., Ltd.) and pre-baked (PRB) on a hot-plateat 100° C. for 1 minute, and their initial blue photo-conversion rateswere measured.

Then, the coated photosensitive resin compositions were radiated by UVwith an exposer (Ghi broadband, Ushio Inc.) with an output (power) of 60mJ/cm² to 100 mJ/cm² and post-baked (POB) in a convection clean oven(Jongro Co., Ltd.) at 180° C. for 30 minutes, and their bluephoto-conversion rates were measured.

As for the pre-baking and the post-baking, a photo-conversion rate fromblue light entering from BLU into green light and a photo maintenancerate were evaluated, and the results are shown in Table 4. Herein, theblue photo-conversion rate (green/blue) was measured by using a CAS 140CT spectrometer equipment and specifically, by putting a bare glass onthe blue BLU (455 nm) covered with a diffusing film to first get areference measured with a detector and then, putting the single filmsobtained by respectively coating the photosensitive resin compositionsaccording to Examples 1 to 9 and Comparative Examples 1 to 4 andmeasuring a blue-to-green converted peak increase amount relative to ablue absorption peak decrease amount. In addition, the photo maintenancerate was also evaluated by measuring how much a photo-conversion rate ofthe initial PRB step was maintained in the POB step (e.g., by measuringhow much the photo-conversion rate was maintained from the PRB step tothe POB step).

TABLE 4 Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Comp. Comp. Comp. Comp. 1 23 4 5 6 7 8 9 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Photo-conversion 23 23 21 20 22 2123 22 23 17 16 16 15 rate (%) Photo Maintenance 95 95 94 93 95 93 94 9595 77 80 81 80 Rate (%)

As shown in Table 4, the photosensitive resin compositions according toExamples 1 to 9 showed a small decrease of blue photo-conversion rateand a high photo maintenance rate during the color filter process ascompared with the photosensitive resin compositions according toComparative Examples 1 to 4.

(Preparation of Curable Composition)

Each curable composition according to Examples 10 to 18 and ComparativeExamples 5 to 8 was prepared to have a composition shown in Tables 5 and6 by using components mentioned therein.

-   -   (A′) Resin    -   (A′-1) Binder Resin    -   Acryl-based resin (TB04, TACOMA)    -   (A′-2) Reactive unsaturated compound    -   Tricyclodecane dimethanol diacrylate (TCI)    -   (B′) Quantum Dot    -   (B′-1) Quantum dot dispersion solution of Preparation Example 1    -   (B′-2) Quantum dot dispersion solution of Preparation Example 7    -   (B′-3) Quantum dot dispersion solution of Preparation Example 8    -   (B′-4) Quantum dot dispersion solution of Preparation Example 9    -   (B′-5) Quantum dot dispersion solution of Preparation Example 10    -   (B′-6) Quantum dot dispersion solution of Preparation Example 11    -   (B′-7) Quantum dot dispersion solution of Preparation Example 12    -   (B′-8) Quantum dot dispersion solution of Preparation Example 13    -   (B′-9) Quantum dot dispersion solution of Preparation Example 14    -   (B′-10) Quantum dot dispersion solution of Comparative        Preparation Example 1    -   (B′-11) Quantum dot dispersion solution of Comparative        Preparation Example 2    -   (B′-12) Quantum dot dispersion solution of Comparative        Preparation Example 3    -   (B′-13) Quantum dot dispersion solution of Comparative        Preparation Example 4    -   (C′) Solvent    -   Propylene glycol monomethylether acetate (PGMEA, Sigma-Aldrich        Corporation)    -   (D′) Diffusion Agent    -   Titanium dioxide dispersion (TiO2 solid: 20 wt %, Average        particle diameter: 200 nm, Ditto Technology)    -   (E′) Polymerization Initiator    -   Thermal polymerization initiator (SAN-AID SI-60, SANSHIN)    -   (F′) Other Additives    -   Leveling agent (F-554, DIC Co., Ltd.)

TABLE 5 (unit: wt %) Ex. Ex. Ex. Ex. Ex. Ex. 10 11 12 13 14 15 Binderresin 9.8 9.8 9.8 9.8 9.8 9.8 Reactive unsaturated 1.6 1.6 1.6 1.6 1.61.6 monomer Polymerization initiator 0.1 0.1 0.1 0.1 0.1 0.1 QuantumB′-1 13 — — — — — dot B′-2 — 13 — — — — B′-3 — — 13 — — — B′-4 — — — 13— — B′-5 — — — — 13 — B′-6 — — — — — 13 Solvent 60.4 60.4 60.4 60.4 60.460.4 Diffusion agent 12.6 12.6 12.6 12.6 12.6 12.6 Other additives 2.52.5 2.5 2.5 2.5 2.5

TABLE 6 (unit: wt %) Ex. Ex. Ex. Comp. Comp. Comp. Comp. 16 17 18 Ex. 5Ex. 6 Ex. 7 Ex. 8 Binder resin 9.8 9.8 9.8 9.8 9.8 9.8 9.8 Reactiveunsaturated monomer 1.6 1.6 1.6 1.6 1.6 1.6 1.6 Thermal polymerizationinitiator 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Quantum B′-7 13 — — — — — — dotB′-8 — 13 — — — — — B′-9 — — 13 — — — — B′-10 — — — 13 — — — B′-11 — — —— 13 — — B′-12 — — — — — 13 — B′-13 — — — — — — 13 Solvent 60.4 60.460.4 60.4 60.4 60.4 60.4 Diffusion agent 12.6 12.6 12.6 12.6 12.6 12.612.6 Other additives 2.5 2.5 2.5 2.5 2.5 2.5 2.5

Evaluation 4: Photo-Conversion Rate and Photo-Maintenance Rate ofQuantum Dot

The curable compositions according to Examples 10 to 18 and ComparativeExamples 5 to 8 were respectively coated into a 1 μm to 2 μm-thick filmon a glass substrate by using a spin-coater (150 rpm, Opticoat MS-A150,Mikasa Co., Ltd.), dried at 80° C. for 1 minute on a hot-plate to obtainfilms, and their initial blue photo-conversion rates were measured (afirst step).

The obtained films were dried in a forced convection drying furnace at220° C. for 40 minutes, and their blue photo-conversion rates weremeasured (a second step).

Regarding the first and second steps, a photo-conversion rate fromincident blue light from BLU to green light and a photo-maintenance ratewere evaluated, and the results are shown in Tables 7 and 8. Herein, theblue photo-conversion rate (green/blue) was obtained by using a CAS 140CT spectrometer and specifically, by putting a bare glass on the blueBLU (455 nm) covered with a diffusing film and first measuring areference with a detector and then, putting the single films obtained byrespectively coating the curable compositions according to Examples 9 to18 and Comparative Examples 5 to 8 and measuring a blue-to-greenconverted peak increase amount relative to a blue absorption peakdecrease amount. In addition, the photo-maintenance rate from the firststep to the second step (e.g., how long the photo-conversion rate in thefirst step was maintained in the second step) was measured.

TABLE 7 Ex. Ex. Ex. Ex. Ex. Ex. Ex. 10 11 12 13 14 15 16Photo-conversion 23 23 21 20 22 21 23 rate (%) Photo-maintenance 95 9594 93 95 93 96 rate (%)

TABLE 8 Ex. Ex. Comp. Comp. Comp. Comp. 17 18 Ex. 5 Ex. 6 Ex. 7 Ex. 8Photo-conversion 23 22 17 16 16 15 rate (%) Photo-maintenance 95 94 7780 81 80 rate (%)

As shown in Tables 7 and 8, the curable compositions according toExamples 10 to 18 showed a small blue photo-conversion ratedeterioration and a high photo-maintenance rate as compared with thecurable compositions according to Comparative Examples 5 to 8, as acolor filter process proceeded.

It will be understood that, although the terms “first,” “second,”“third,” etc., may be used herein to describe various elements,components, regions, layers and/or sections, these elements, components,regions, layers and/or sections should not be limited by these terms.These terms are used to distinguish one element, component, region,layer or section from another element, component, region, layer orsection. Thus, a first element, component, region, layer or sectiondescribed below could be termed a second element, component, region,layer or section, without departing from the spirit and scope of thepresent disclosure.

Spatially relative terms, such as “beneath,” “below,” “lower,” “under,”“above,” “upper,” and the like, may be used herein for ease ofexplanation to describe one element or feature's relationship to anotherelement(s) or feature(s) as illustrated in the figures. It will beunderstood that the spatially relative terms are intended to encompassdifferent orientations of the device in use or in operation, in additionto the orientation depicted in the figures. For example, if the devicein the figures is turned over, elements described as “below” or“beneath” or “under” other elements or features would then be oriented“above” the other elements or features. Thus, the example terms “below”and “under” can encompass both an orientation of above and below. Thedevice may be otherwise oriented (e.g., rotated 90 degrees or at otherorientations) and the spatially relative descriptors used herein shouldbe interpreted accordingly.

It will be understood that when an element or layer is referred to asbeing “on,” “connected to,” or “coupled to” another element or layer, itcan be directly on, connected to, or coupled to the other element orlayer, or one or more intervening elements or layers may be present. Inaddition, it will also be understood that when an element or layer isreferred to as being “between” two elements or layers, it can be theonly element or layer between the two elements or layers, or one or moreintervening elements or layers may also be present.

The terminology used herein is for the purpose of describing particularembodiments only and is not intended to be limiting of the presentdisclosure. As used herein, the singular forms “a” and “an” are intendedto include the plural forms as well, unless the context clearlyindicates otherwise. It will be further understood that the terms“comprises,” “comprising,” “includes,” and “including,” when used inthis specification, specify the presence of the stated features,integers, acts, operations, elements, and/or components, but do notpreclude the presence or addition of one or more other features,integers, acts, operations, elements, components, and/or groups thereof.As used herein, the term “and/or” includes any and all combinations ofone or more of the associated listed items. Expressions such as “atleast one of,” when preceding a list of elements, modify the entire listof elements and do not modify the individual elements of the list.

As used herein, the terms “substantially,” “about,” and similar termsare used as terms of approximation and not as terms of degree, and areintended to account for the inherent deviations in measured orcalculated values that would be recognized by those of ordinary skill inthe art. Further, the use of “may” when describing embodiments of thepresent disclosure refers to “one or more embodiments of the presentdisclosure.” As used herein, the terms “use,” “using,” and “used” may beconsidered synonymous with the terms “utilize,” “utilizing,” and“utilized,” respectively. Also, the term “exemplary” is intended torefer to an example or illustration.

Also, any numerical range recited herein is intended to include allsub-ranges of the same numerical precision subsumed within the recitedrange. For example, a range of “1.0 to 10.0” is intended to include allsubranges between (and including) the recited minimum value of 1.0 andthe recited maximum value of 10.0, that is, having a minimum value equalto or greater than 1.0 and a maximum value equal to or less than 10.0,such as, for example, 2.4 to 7.6. Any maximum numerical limitationrecited herein is intended to include all lower numerical limitationssubsumed therein, and any minimum numerical limitation recited in thisspecification is intended to include all higher numerical limitationssubsumed therein. Accordingly, Applicant reserves the right to amendthis specification, including the claims, to expressly recite anysub-range subsumed within the ranges expressly recited herein.

While the subject matter of the present disclosure has been described inconnection with what is presently considered to be practical exampleembodiments, it is to be understood that the present disclosure is notlimited to the disclosed embodiments, but, on the contrary, is intendedto cover various modifications and equivalent arrangements includedwithin the spirit and scope of the appended claims, and equivalentsthereof. Therefore, the aforementioned embodiments should be understoodto be exemplary and not limiting the present disclosure in any way.

What is claimed is:
 1. A photosensitive composition, comprising: (A) abinder resin; (B) a photopolymerizable monomer; (C) aphotopolymerization initiator; (D) a quantum dot surface-modified with afirst compound having a thiol group at one terminal end or at the middleof a main chain and having an alkoxy group, a cycloalkyl group, acarboxyl group, or a hydroxy group at the other terminal end or a secondcompound having each thiol group at one terminal end and at the middleof the main chain and having an alkoxy group, a cycloalkyl group, acarboxyl group, or a hydroxy group at the other terminal end; and (E) asolvent.
 2. The photosensitive composition of claim 1, wherein thealkoxy group is a C1 to C10 alkoxy group and the cycloalkyl group is aC3 to C10 cycloalkyl group.
 3. The photosensitive composition of claim1, wherein the first compound and second compound each independentlycomprises an ester group.
 4. The photosensitive composition of claim 3,wherein the first compound is represented by Chemical Formula 1 and thesecond compound is represented by Chemical Formula 2:

wherein, in Chemical Formula 1 and Chemical Formula 2, R¹ is asubstituted or unsubstituted C1 to C20 alkyl group, a substituted orunsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C3to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 arylgroup, or a substituted or unsubstituted lactone ring, L¹ and L² areindependently a single bond, a substituted or unsubstituted C1 to C20alkylene group, a substituted or unsubstituted C1 to C20 oxyalkylenegroup, or a combination thereof, and n is an integer of 1 or
 2. 5. Thephotosensitive composition of claim 4, wherein the lactone ring is a5-membered ring or a 6-membered ring.
 6. The photosensitive compositionof claim 4, wherein in Chemical Formula 2, L² is a C1 to C20 alkylenegroup substituted with a thiol group.
 7. The photosensitive compositionof claim 4, wherein the substituted or unsubstituted C1 to C20oxyalkylene group is a substituted or unsubstituted oxymethylene group,a substituted or unsubstituted oxyethylene group, or a combinationthereof.
 8. The photosensitive composition of claim 7, wherein theoxymethylene group is represented by Chemical Formula 3 and theoxyethylene group is represented by Chemical Formula 4:

wherein, in Chemical Formula 3 and Chemical Formula 4, m is an integerof 1 to
 5. 9. The photosensitive composition of claim 1, wherein thefirst compound is represented by one of Chemical Formula 1-1 to ChemicalFormula 1-7 and the second compound is represented by Chemical Formula2-1:

in Chemical Formula 1-3 to Chemical Formula 1-6, m is an integer of 1 to5,


10. The photosensitive composition of claim 1, wherein thesurface-modified quantum dot has a core-shell structure wherein theshell comprises Zn, and the thiol group at the terminal end of thecompound represented by Chemical Formula 1 or Chemical Formula 2 isbonded with Zn of the shell.
 11. The photosensitive composition of claim1, wherein the quantum dot has a maximum fluorescence wavelength in awavelength range of 500 nm to 680 nm.
 12. The photosensitive compositionof claim 1, wherein the solvent comprises propylene glycolmonomethylether acetate, dipropylene glycol methylether acetate,ethanol, ethylene glycoldimethylether, ethylenediglycolmethylethylether, diethylene glycoldimethylether,2-butoxyethanol, N-methylpyrrolidine, N-ethylpyrrolidine, propylenecarbonate, γ-butyrolactone, or a combination thereof.
 13. Thephotosensitive composition of claim 1, wherein the binder resincomprises an acryl-based binder resin, a cardo-based binder resin, or acombination thereof.
 14. The photosensitive composition of claim 1,wherein the photosensitive composition further comprises (F) a diffusionagent.
 15. The photosensitive composition of claim 14, wherein thediffusion agent is included in an amount of 0.1 wt % to 20 wt % based onthe total amount of the photosensitive composition.
 16. Thephotosensitive composition of claim 14, wherein the diffusion agentcomprises barium sulfate, calcium carbonate, titanium dioxide, zirconia,or a combination thereof.
 17. The photosensitive composition of claim 1,wherein the photosensitive composition comprises 1 wt % to 30 wt % ofthe (A) binder resin; 0.1 wt % to 30 wt % of the (B) photopolymerizablemonomer; 0.1 wt % to 10 wt % of the (C) photopolymerization initiator; 1wt % to 40 wt % of the (D) surface-modified quantum dot; and a balanceamount of the (E) solvent based on the total amount of thephotosensitive composition.
 18. The photosensitive composition of claim1, wherein the photosensitive composition further comprises malonicacid; 3-amino-1,2-propanediol; a silane-based coupling agent; a levelingagent; a fluorine-based surfactant; a polymerization inhibitor; or acombination thereof.
 19. A method of manufacturing a surface-modifiedquantum dot comprising: dispersing quantum dots surface-modified witholeic acid in a nonpolar solvent; adding a compound having a thiol groupat one terminal end and an alkoxy group, a cycloalkyl group, a carboxylgroup, or a hydroxy group at the other terminal end, and a metal saltthereto and stirring the same; and centrifuging the stirred solution toseparate a supernatant and lower liquid followed by drying the lowerliquid.
 20. The method of claim 19, wherein the metal salt is ZnCl₂. 21.The method of claim 19, wherein the stirring is performed at atemperature of 60° C. to 70° C.
 22. A color filter manufactured by usingthe photosensitive composition of claim 1.